CN104593053B - Adsorption desulphurization reaction apparatus and adsorption desulphurization method - Google Patents
Adsorption desulphurization reaction apparatus and adsorption desulphurization method Download PDFInfo
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- CN104593053B CN104593053B CN201310528628.4A CN201310528628A CN104593053B CN 104593053 B CN104593053 B CN 104593053B CN 201310528628 A CN201310528628 A CN 201310528628A CN 104593053 B CN104593053 B CN 104593053B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention provides an adsorption desulphurization reaction apparatus and application thereof. A fluidized bed reactor in the apparatus comprises a reactor main body with sealed top, a spiral-flow type gas-solid separator and a gas guide pipe; and the upper part at a straight cylinder area of the spiral-flow type gas-solid separator is provided with at least two air intake guiding channels along the tangential direction, and the contour of each air intake guiding channel is a spiral curve. The invention further provides an adsorption desulphurization method. The adsorption desulphurization reaction apparatus is capable of effectively reducing suspension concentration of a catalyst fine powder in a settlement space of the reactor, timely transferring the catalyst fine powder generated in the reaction process out of the reaction system, avoiding accumulation of the catalyst fine powder in the fluidized bed reactor, keeping stable long-term operation and obtaining good and stable reaction effect. The spiral-flow type gas-solid separator generates small wearing on a catalyst particle, and is capable of obviously reducing catalyst consumption and reducing operation cost of the apparatus when being used as a reactor for adsorption desulphurization.
Description
Technical field
The present invention relates to a kind of absorption desulfuration reaction device, the invention still further relates to a kind of desulfurizing method by adsorption.
Background technology
Along with environmental requirement is improved constantly by countries in the world, the index of content of sulfur in gasoline is the strictest.This is just to vapour
Oil desulfurization technology is had higher requirement.Dividing from structure of reactor, current gasoline desulfurization technology mainly has fixed bed desulfurization
With two kinds of methods of fluid-bed sweetening.
Fixed bed desulfurization has hydrofinishing and absorption two kinds of methods of desulfurization, and the former can be because of gasoline olefin and virtue in hydrogenation process
Hydrocarbon saturated, causes octane number to lose, and the deep desulfurization of gasoline that especially olefin(e) centent is high can make octane number lose
Bigger；There is Catalysts Deactivation Problems in the latter, needs catalyst frequent regeneration.
The Typical Representative of fluid-bed sweetening is the S-Zorb technique of Cophi Co., Ltd of U.S. exploitation, and this technique is that a kind of reaction is inhaled
Attached sulfur removal technology, combines fluidized-bed reactor and cyclic regeneration technology, solves the deactivation prob of fixed bde catalyst.Phase
For ADSORPTION IN A FIXED BED desulfurization, fluid-bed sweetening has solid particle and the mix homogeneously of gas, does not results in local run aways
Advantage.
Existing S-Zorb absorption desulfurization technology uses fluidized absorption reactor, and product is arranged by reactor head
Dust filter unit leave reactor, solid particle is then drawn by being arranged on drainage conduit below the Bed level of reactor top
Reactor, enters in regenerator and restorer and carries out regenerating and reducing.But, in the reactor of fluidized absorption, thin in catalyst
The fine powder that powder and granule long term wear produce is by the settlement space long-term suspension of elutriation to fluid bed so that particle does not has machine
Fluid bed dense-phase bed can be returned to, reactor can not be discharged, get off for a long time and then affect the stable operation of device.
For eliminating beds top dilute phase space granule long-term suspension and gas solid separation problem in fluidized-bed reactor,
Conventional flow fluidized bed reactor arranges cyclone separator to reclaim solid particle at top.But general cyclone separator requires to enter rotation
The gas speed of wind separator is in the range of 15-25m/s, and height enters implication speed and is no doubt conducive to improving gas-solid efficiency, but can increase
The abrasion of grain.And gasoline absorbing desulfurization used catalyst mechanical strength is relatively low, if arranging tradition in the reactor of fluidized absorption
Cyclone separator, then relatively big because entering implication speed, the abrasion of catalyst granules can be aggravated, and then the operation being greatly improved device becomes
This.
Accordingly, it is desirable to provide a kind of new absorption desulfuration reaction device, this reaction unit can not only realize adsorbing desulfurization,
And the catalyst fines formed in fluidized-bed reactor can be removed reaction system in time, reduce fluidized-bed reactor sedimentation
The amount of the catalyst granules suspended in district, will not aggravate the abrasion of catalyst granules simultaneously, it is achieved stable, the long period fortune of device
Turn.
Summary of the invention
The catalyst fines existed for the desulfurizing fluid bed reaction unit of existing absorption is in the sedimentation of fluidized-bed reactor
Space long-term suspension, affects the technical problem of plant running stability, the invention provides a kind of absorption desulfuration reaction device, should
Catalyst fines can be removed reaction system by absorption desulfuration reaction device in time, reduces in fluidized-bed reactor decanting zone and suspends
The amount of catalyst granules, and the abrasion of catalyst granules will not be aggravated, it is achieved stable, the long-term operation of device.
The invention provides a kind of absorption desulfuration reaction device, this device includes fluidized-bed reactor, fine powder collector, again
Raw device and restorer, described fluidized-bed reactor is used for contacting sulfur-bearing hydrocarbon feed with the catalyst with absorption desulfidation,
And export oil agent mixture；Described fine powder collector is for isolating the catalyst fines in described oil agent mixture；Described again
Raw device is for by the catalyst regeneration of inactivation；Described restorer is for sending the catalyst reduction Posterior circle of regeneration into described fluidisation
In bed reactor；
Wherein, described fluidized-bed reactor include seal reactor body, at least one cyclone type gas-solid separator and
Airway；
The inner space of described reactor body includes reaction zone and decanting zone from bottom to top；
The main body of described cyclone type gas-solid separator is the hollow structure that top seals, and its inner space includes from top to bottom
Straight tube district and pyramidal area, the main body of described cyclone type gas-solid separator is arranged in described decanting zone, and described cyclone type gas-solid divides
Discharging opening from device is positioned at the bottom of described pyramidal area and extends downward in described reaction zone, the air inlet position of described airway
In described straight tube district, the gas outlet of described airway is positioned at the outside of described fluidized-bed reactor, the top in described straight tube district
Tangentially being provided with at least two and guide air intake passage, the contour line of described guiding air intake passage is spiral curve.
Present invention also offers a kind of desulfurizing method by adsorption, the method is in the absorption desulfuration reaction device that the present invention provides
Carry out, including: by sulfur-bearing hydrocarbon feed with have absorption desulfidation catalyst in the reaction zone of described fluidized-bed reactor
Contact, to remove at least part of element sulphur in described sulfur-bearing hydrocarbon feed；The oil agent mixture that fluidized-bed reactor exports is existed
Fine powder collector separates, obtains the catalyst fines of oil gas product and recovery；By thin for the catalyst that at least partly reclaims
Powder circulation is sent in described reaction zone；Decaying catalyst is sent in described regenerator and regenerates, obtain regenerated catalyst；Will
The Posterior circle that reduces in the described regenerated catalyst described restorer of feeding is sent in the reaction zone of described fluidized-bed reactor.
Fluidized bed reaction according to the present invention can effectively reduce catalyst in the settlement space of fluidized-bed reactor
The suspended concentration of fine powder, and the catalyst fines removal response system that will produce in course of reaction in time, it is to avoid catalyst fines
Accumulation in a fluidized bed reactor so that reaction unit can stablize long-term operation, thus obtain good and stable anti-
Answer effect.
Further, the cyclone type gas-solid separator used in the absorption desulfuration reaction device of the present invention mill to catalyst granules
Damage little, it is possible to substantially reduce the consumption of catalyst, thus reduce the operating cost of device.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not intended that limitation of the present invention.
Fig. 1 is for illustrating a kind of embodiment of the absorption desulfuration reaction device of the present invention.
Fig. 2 is for illustrating according to the cyclone type gas-solid separator used in the reaction unit of the present invention.
Fig. 3 leads to according to the guiding air intake of the cyclone type gas-solid separator used in the reaction unit of the present invention for explanation
Road.
The one side of being preferable to carry out of the cyclone type gas-solid separator that Fig. 4 uses in the reaction unit that the present invention is described
Formula.
Fig. 5 is the top view of the preferred implementation described in Fig. 4.
Fig. 6 inner member in the fluidized-bed reactor that the present invention is described.
Fig. 7 is for illustrating that in the fluidized-bed reactor of the present invention, the one of inner member is preferred embodiment.
Description of reference numerals
1: reactor body 11: reaction zone
12: decanting zone 13: direct tube section
14: extension diameter section 2: cyclone type gas-solid separator
21: straight tube district 22: pyramidal area
23: guiding air intake passage 3: kuppe
4: airway 5: material input pipe
6: catalyst input pipe 7: reclaimable catalyst outlet tube
8: inner member 81: fixed plate
82: baffle plate 811: outer ring plate
812: dividing plate 9: fluidized-bed reactor
10: fine powder collector 101: agent structure
102: filter 103: oil gas vent
104: recovery catalyst transport pipeline 105: catalyst transport arm
210: the first cyclone type gas-solid separators 211: straight tube district
212: pyramidal area 213: guide air intake passage
214: discharging opening 210: primary cyclone
220: the second cyclone type gas-solid separators 221: straight tube district
222: pyramidal area 223: guide air intake passage
224: discharging opening
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
In the present invention, if not otherwise specified, term "up" and "down" is on the basis of the flow direction of charging.
The invention provides a kind of absorption desulfuration reaction device, as it is shown in figure 1, this device includes fluidized-bed reactor 9, thin
Powder catcher 10, regenerator (not shown) and restorer (not shown).
As it is shown in figure 1, this fluidized-bed reactor includes that the reactor body 1 sealed, at least one cyclone type gas-solid separate
Device 2 and airway 4.
As it is shown in figure 1, the inner space of reactor body 1 includes reaction zone 11 and decanting zone 12, spiral-flow type from bottom to top
The main body of gas-solid separator 2 is arranged in decanting zone 12.
In the present invention, described reaction zone refers to for by reactant and the catalytic space of catalyst, described decanting zone
Refer to for accommodating the oil agent mixture coming from reaction zone, and make the catalyst granules that the granularity in oil agent mixture is bigger sink
The space of reaction zone drops and returns.
Reaction zone 11 can be straight barrel type reaction zone, it is also possible to for reducing reaction zone, preferably reducing reaction zone, more preferably
For reducing cylinder reaction zone.When reaction zone 11 is reducing reaction zone, as it is shown in figure 1, reaction zone 11 preferably includes direct tube section
13 and extension diameter section 14.The outer contour of extension diameter section 14 and the angle α of horizontal plane can be conventional selection.Usually, extension diameter section 14
The angle α of outer contour and horizontal plane can be 30～75 °, preferably 35～60 °.
The various inner members for strengthening gas-particle two-phase contact commonly used in the art can be set in described reaction zone.
The shape of decanting zone 12 can be the conventional selection of this area, to be capable of the catalyst granules making granularity bigger
Settle and return reaction zone 11 to be as the criterion.Usually, decanting zone 12 is cylindrical shape.
Reaction zone 11 and the ratio of the cross-sectional area of decanting zone 12 can be conventional selection.The cross-sectional area of reaction zone 11
For A11, the cross-sectional area of decanting zone 12 is A12, usually, A12/A11Can be 1.2～6, preferably 1.5～4.In reaction zone
11 when being reducing reaction zone, A11Refer to the cross-sectional area of direct tube section in reaction zone.
As it is shown in figure 1, described fluidized-bed reactor is additionally provided with material input pipe 5 and catalyst input pipe 6.Material inputs
Pipe 5 is positioned at the bottom of fluidized-bed reactor, sends into the reaction zone 11 of fluidized-bed reactor for feeding (that is, treating material)
In with catalyst haptoreaction.Material input pipe 5 is general with the material distributor (not shown) being arranged on reaction zone 11 inner bottom part
It is connected, so that charging is even in reaction zone.Catalyst input pipe 6 is generally located on the lower sides of reaction zone, is used for
Being sent into by catalyst in reaction zone 11, its other end typically connects with catalyst regeneration reducing unit.
As it is shown in figure 1, be provided with reclaimable catalyst outlet tube 7 in the upper portion side wall of reaction zone 11, for by catalysis to be generated
Agent is sent in catalyst regeneration reducing unit and is carried out regenerating and reducing.Reclaimable catalyst outlet tube 7 is positioned at the material of beds
Under face, in order to conveying reclaimable catalyst.
As it is shown in figure 1, the main body of cyclone type gas-solid separator 2 is arranged in decanting zone 12, for decanting zone will be come from
Gas mixture in the oil agent mixture of 12 is separated, and isolated gas mixture is sent fluidized-bed reactor,
The catalyst granules concurrently separated out returns in reaction zone 11 along the discharging opening of cyclone type gas-solid separator.
As in figure 2 it is shown, the main body of cyclone type gas-solid separator 2 is the hollow structure that top seals, its inner space is from upper
Straight tube district 21 and pyramidal area 22 is included under and.
As illustrated in fig. 1 and 2, the air inlet of airway 4 is positioned in straight tube district 21, the body hermetically passing eddy flow of airway 4
The top of formula gas-solid separator 2 and the top of fluidized-bed reactor, so that gas outlet is positioned at the outside of fluidized-bed reactor, be used for
Isolated for cyclone type gas-solid separator 2 gas mixture is sent fluidized-bed reactor.
As in figure 2 it is shown, the straight tube district 21 of cyclone type gas-solid separator is connected with pyramidal area 22.Straight tube district 21 and pyramidal area 22
Cross section be circular.The height H in straight tube district 2121Height H with pyramidal area 2222Ratio H21/H22Can be 0.4～1.5.
Under conditions of the volume taking into account cyclone type gas-solid separator, separate separating effect from improving further, reduce thickness powder and carry secretly
The angle of degree is set out, the height H in straight tube district 2121Height H with pyramidal area 2222Ratio H21/H22Preferably 0.5～1, more
It is preferably 0.5～0.8.
As shown in Figures 2 and 3, the top in straight tube district 21 is tangentially provided with at least two and guides air intake passage 23, decanting zone
Oil agent mixture in 12 is entered in the straight tube district 21 of cyclone type gas-solid separator by this guiding air intake passage 23 and sorts
Separate.Be conducive in straight tube district 21, form uniform and stable air-flow by arranging at least two guiding air intake passage 23, improve
Separate the efficiency of separation.The quantity guiding air intake passage 23 is preferably 3～8.Preferably, the air intake passage circumference in straight tube district is guided
For being uniformly arranged on direction.
As it is shown on figure 3, the contour line guiding air intake passage 23 is spiral curve, it is, guide the wheel of air intake passage 23
Profile is to guide port that air intake passage 23 connects with straight tube district 21 as original position, and this port moves formation along spiral curve
Track.Be directed to the contour line of air intake passage 23 be designed as spiral curve can be by means of the centrifugal work produced in flow process
With, logistics is carried out pre-separation, makes the relatively large solid particle of the quality in logistics closer to the inwall of passage, thus improve point
From efficiency.Further, be directed to air intake passage 23 be designed as spiral curve can also be effectively prevented from fluid flowing turbulent perturbation,
Prior it is possible to avoids the solid particle in material to wash away collision channel inwall, on the one hand reduces the erosion degree of inwall,
On the other hand reduce bounce-back and the back-mixing of solid particle, alleviate abrasion and the degree of crushing of solid particle.
Guiding air intake passage 23 can be to be horizontally disposed with, it is also possible to for there is certain angle between horizontal plane.Preferably
Guiding air intake passage 23 is to there is certain angle between horizontal plane.Specifically, as shown in Figure 4, by guiding air intake passage 23
Arrival end on a little determine with point corresponding with this point on the port that straight tube district 21 connects with guiding air intake passage 23
The angle theta of straight line and horizontal plane can be 0～45 °, preferably 5～30 °.
The area of the entrance guiding air intake passage 23 is A231, guide the port that connects with straight tube district 21 of air intake passage 23
Area is A232, A231/A232Can be 1～5.The present invention one preferred embodiment in, guide air intake passage 23 wheel
Profile is logarithmic spiral curve, it is, guide air intake passage 23 from arrival end to straight tube district 21, its cross-sectional area is for gradually to become
Little.It is highly preferred that A231/A232It is 1.2～2.5.
The contour line that conventional various methods can be used to be directed to air intake passage 23 is processed into spiral curve, the most no longer
Describe in detail.
In a preferred embodiment, it is also possible to arrange and guide the undergauge that the arrival end of air intake passage is tightly connected
Passage (not shown), along charging flow direction in this undergauge passage, the cross-sectional area of this undergauge passage is gradually reduced.Logical
Cross the arrival end guiding air intake passage and undergauge passage is set, it is possible to increase enter the speed of the logistics guiding air intake passage.Should
The cross-sectional area of the arrival end of undergauge passage and the cross section face of its port of export (that is, the port connected with guiding air intake passage)
Long-pending ratio can be 1.1～2, preferably 1.2～1.5.
Guide air intake passage 23 and be arranged on the top in straight tube district 21, be preferably directed upper limb and the straight tube district 21 of air intake passage 23
Top concordant.
The cross section guiding air intake passage 23 can be various suitable shape, as circular or square.
The quantity of described cyclone type gas-solid separator can be one or more, and the quantity of separator can be according to instead
The treating capacity answering device carries out suitable selection, the oil agent mixture produced in course of reaction can be separated in time and will separate
The oil gas product gone out is sent reactor and is as the criterion.The present invention one preferred embodiment in, as shown in Figure 4 and Figure 5, eddy flow
Formula gas-solid separator 2 includes the first cyclone type gas-solid separator 210 and the second cyclone type gas-solid separator 220, the second spiral-flow type
Gas-solid separator 220 is arranged in the main body of the first cyclone type gas-solid separator 210, and airway 4 air inlet is positioned at the second eddy flow
In the straight tube district 221 of formula gas-solid separator 220.Two cyclone type gas-solid separator nestings are used and can improve separation further
The efficiency of separation.
According to this preferred embodiment, the internal diameter (for interior diameter) of airway 4 is D4, the lower edge of airway 4 is to second
The distance on the lower edge guiding air intake passage 223 of cyclone type gas-solid separator 220 is H1, H1/D4Generally 0～3, preferably 0.2
～1.5, more preferably 0.4～1.According to this preferred embodiment, the top of the second cyclone type gas-solid separator 220 is to first
The distance from top of cyclone type gas-solid separator 210 is to enable to the guiding air intake passage of the second cyclone type gas-solid separator 220
The fluid of the porch of 223 is in the eddy flow stage, so that fluid enters the second cyclone type gas-solid separator 220 along eddy flow direction
Separated region.Usually, the top of the second cyclone type gas-solid separator 220 to the top of the first cyclone type gas-solid separator 210
Distance be H2, the internal diameter of airway 4 is D4, H2/D4=0～10.
According to this preferred embodiment, the discharging opening 224 of the second cyclone type gas-solid separator 220 extends to the first eddy flow
In the discharging opening 214 of formula gas-solid separator 210.The discharging opening 224 development length in discharging opening 214 is to guarantee not result in
Gas in one cyclone type gas-solid separator 210 seals in the discharging opening 224 of the second cyclone type gas-solid separator 220 and is as the criterion.
Usually, the discharging opening 224 of the second cyclone type gas-solid separator 220 is at the discharging opening 214 of the first cyclone type gas-solid separator 210
In development length be L224, a length of L of the discharging opening 214 of the first cyclone type gas-solid separator 210214, L224/L214Can be
0.4～1, preferably 0.5～0.8.
Another preferred embodiment according to the present invention, it is also possible to straight at least one cyclone type gas-solid separator
Cylinder arranges kuppe in district.Described kuppe is tubular, and its upper end is connected with the top of cyclone type gas-solid separator, and lower end is spacious
On the one hand mouth structure, can lead into the logistics in straight tube district and move downward along the inwall in straight tube district, on the other hand can guide
Moved upward by the isolated eddy flow of cyclone type gas-solid separator, and left the inside sky of fluidized-bed reactor by airway
Between.
The height of described kuppe is not more than the height in straight tube district.Usually, the height of kuppe and the height in straight tube district
Ratio can be 0.4～1, preferably 0.6～0.9.
(that is, the isolated logistics of inward eddy that the internal diameter of described kuppe should be greater than producing in cyclone type gas-solid separator
The eddy flow formed) diameter, thus avoid inward eddy and contour stealth (that is, to enter what the logistics of cyclone type gas-solid separator was formed
Eddy flow) interfere.Usually, the internal diameter in straight tube district can be 1:0.4～0.8 with the ratio of the internal diameter of kuppe, is preferably
1:0.5～0.75.
The first cyclone type gas-solid separator and second of previously described nesting is included at described cyclone type gas-solid separator
During cyclone type gas-solid separator, as shown in Figure 4, can only arrange in the straight tube district 211 of the first cyclone type gas-solid separator 210
Kuppe 3.Now, kuppe 3 is arranged in the straight tube district 211 of the first cyclone type gas-solid separator 210, and outside kuppe 3
Existential Space between the inwall of wall and the first cyclone type gas-solid separator 210, inwall and second cyclone type gas-solid of kuppe 3 divide
Existential Space between the outer wall of device 220.Usually, the internal diameter of kuppe 3 is D3, the first cyclone type gas-solid separator 210
The internal diameter in straight tube district 211 is D211, the internal diameter in the straight tube district 221 of the second cyclone type gas-solid separator 220 is D221, D211: D3: D221
Can be 1.25～2.5:1:0.4～0.8, preferably 1.3～2:1:0.4～0.6.The height of kuppe 3 is H3, the first eddy flow
The height in the straight tube district 211 of formula gas-solid separator 210 is H211, the height in the straight tube district 221 of the second cyclone type gas-solid separator 220
Degree is H221, H211: H3: H221Can be 1～2.5:1:0.4～1, preferably 1～2:1:0.5～0.8.
In described fluidized-bed reactor, for receiving the arrival end guiding air intake passage of the logistics coming from decanting zone
The gross area is At 23, the area of the horizontal cross-section of described decanting zone is A12, the area of the radial section of described airway is A4,
At 23: A12: A4It is preferably 0.01～0.4:1:0.01～0.04, more preferably 0.05～0.2:1:0.02～0.25.So can
The gas speed entered in cyclone type gas-solid separator is controlled in the reasonable scope, catalyst particles in separation process can be reduced further
There is broken probability in grain, can also obtain good separating effect simultaneously.Specifically, it is being used as to inhale by this fluidized-bed reactor
During the reactor of attached desulfurization, under conditions of the apparent linear velocity of sulfur-bearing hydrocarbon feed is 0.1～0.6m/s, come from described decanting zone
Oil agent mixture be generally 1～8m/s in the arrival line speed of the arrival end of described guiding air intake passage.
" for receiving the gross area guiding air intake passage of the logistics coming from decanting zone " is to instigate to come from decanting zone
Logistics enter the area sum of arrival end guiding air intake passage of cyclonic separator.Such as, at described cyclone type gas-solid
When separator includes previously described first cyclone type gas-solid separator and the second cyclone type gas-solid separator, for receive from
The guiding air intake passage of the logistics in decanting zone refers to entering of the whole guiding air intake passage on the first cyclone type gas-solid separator
The area sum of mouth end.
The present invention one preferred embodiment in, as it is shown in figure 1, described fluidized-bed reactor also includes at least one
Individual inner member 8, inner member 8 is arranged on reaction zone 11 and the intersection of decanting zone 12, is used for stopping in beds and is kicked up
Catalyst granules enter decanting zone, reduce further the suspension amount of catalyst fines in decanting zone.
As shown in Figure 6, inner member 8 can include fixed plate 81 and multiple baffle plate 82, and the two ends of baffle plate 82 are respectively with solid
Determining that plate 81 is fixing to be connected, fixed plate 81 is along the longitudinally disposed of reactor body 1 and fixing with reactor body 1 is connected, fixed plate
The outer wall of 81 preferably connects with the inwall of reactor body, and baffle plate 82 is along the horizontally set of reactor body 1 and relative to level
Face, for being obliquely installed, is arranged for interval between adjacent screen.The oil agent mixture so generated in reaction zone can pass through interior structure
Part 8 enters in decanting zone 12, and the catalyst granules kicked up in beds then can be due to baffle plate 82 in inner member 8
Barrier effect returns in beds, further the suspension amount of the catalyst fines in minimizing decanting zone 12.
Multiple baffle intervals are arranged, and on the one hand make the oil agent mixture generated in reaction zone pass through, and on the other hand stop and urge
The catalyst granules kicked up in agent bed enters decanting zone.Preferably, described baffle plate angle of inclination with respect to the horizontal plane makes
The lower edge projection in the horizontal plane of the projection in the horizontal plane of upper edge and adjacent screen of baffle plate overlaps, so can be more preferable
Stop in beds that the catalyst granules kicked up enters in decanting zone.
Fixed plate for multiple baffle plates being formed as an entirety and being fixed in reactor body, can be various can
Realize the component of above-mentioned functions.Such as: as shown in Figure 6, fixed plate 81 can be an annular slab, the two ends of baffle plate 82 and this ring
The inwall of shape plate is fixing to be connected.In a preferred embodiment, as it is shown in fig. 7, fixed plate includes that outer ring plate 811 is with mutual
Vertically disposed two dividing plates 812, dividing plate 812 be arranged in the space that outer ring plate 811 surrounds and two ends respectively with outer ring plate 811
Inwall fixing connect, the two ends of baffle plate 82 respectively with the inwall of outer ring plate 811 and dividing plate 812 is fixing is connected.By at outer shroud
Plate arranges dividing plate the inner space of outer ring plate is divided into four regions, be perfectly even divided into four regions, baffle plate is set respectively
Put in these four regions, it is possible to shorten the length of baffle plate, improve inner member and stop the ability of the catalyst granules kicked up.
Owing to inner member is arranged between reaction zone and decanting zone, and the discharging opening of cyclone type gas-solid separator needs to extend
To reaction zone, therefore on inner member, position corresponding with the discharging opening of cyclone type gas-solid separator offers for spiral-flow type
The hole (not shown) that the discharging opening of gas-solid separator passes through.
As it is shown in figure 1, the material inlet of fine powder collector 10 connects with the airway 4 of fluidized-bed reactor 9, it is used for separating
Go out the catalyst fines carried secretly in described gas mixture, and use the catalyst circulation required to send into stream by remaining able to meet
In fluidized bed reactor 9.Fine powder collector 10 can be conventional various can to isolate catalyst fines from gas mixture
Device.Specifically, fine powder collector 10 can be included as the agent structure 101 of hollow structure, the inside of this agent structure 101
Space from top to bottom includes straight tube district and pyramidal area, is provided with filter 102 on the top (preferred top) in straight tube district, enters thin
Catalyst fines therein is separated by the gas mixture of powder catcher 10 by filter 102, the oil gas product obtained
Send in follow-up processing unit by being arranged on the oil gas vent 103 at agent structure 101 top, isolated catalyst fines
Fall in pyramidal area the most under gravity, and eventually through the recovery catalyst transport pipeline being arranged on bottom pyramidal area
104 outputs.The catalyst fines reclaimed remain able to meet reaction require time, can be thin by the catalyst at least partly reclaimed
Powder is sent into by reclaiming catalyst transport arm 105 circulation in the reaction zone of fluidized-bed reactor 9；At the catalyst fines reclaimed
Use cannot be met when requiring, then send in catalyst fines storage facility.
Filter 102 can be conventional various can to isolate catalysis from the oil gas product being entrained with catalyst fines
The filter of agent fine powder, such as wire gauze filter or metal filter candle filter.Preferably, filter 102 is additionally provided with automatically
Back-blowing device, so can blow off the catalyst fines being deposited on filter 102 by periodically turning on automatic back blow device,
Prevent filter blocked.
Described regenerator is for by the catalyst regeneration of inactivation；Described restorer is for following after the catalyst reduction of regeneration
Ring is sent in described fluidized-bed reactor.Can use the usual manner of this area by described regenerator and catalyst reducer with
The inner space connection of fluidized-bed reactor, thus be delivered to reclaimable catalyst in regenerator regenerate, and by after reduction
Catalyst circulation send into fluidized-bed reactor reaction zone in.Described regenerator and restorer can be the conventional choosing of this area
Select, the most no longer describe in detail.
Present invention also offers a kind of desulfurizing method by adsorption, the method is in the absorption desulfuration reaction device that the present invention provides
Carry out, including: by sulfur-bearing hydrocarbon feed with have absorption desulfidation catalyst in the reaction zone of described fluidized-bed reactor
Contact, to remove at least part of element sulphur in described sulfur-bearing hydrocarbon feed；The oil agent mixture that fluidized-bed reactor exports is existed
Particle collector separates, obtains the catalyst fines of oil gas product and recovery；At least part of catalyst fines is circulated
Send in described reaction zone；Decaying catalyst is sent in described regenerator and regenerates, obtain regenerated catalyst；By described again
The Posterior circle that reduces in the raw catalyst described restorer of feeding is sent in the reaction zone of described fluidized-bed reactor.
Described absorption desulfuration reaction device and structure thereof have been carried out detailed description above, the most no longer describe in detail.
The present invention is not particularly limited for the kind of described sulfur-bearing hydrocarbon feed, can be the common various needs in this area
Carry out adsorbing the sulfur-bearing hydrocarbon feed of desulfurization.Preferably, described sulfur-bearing hydrocarbon feed is in direct steaming gasoline, catalytic gasoline and coker gasoline
One or more.
Described there is absorption desulfidation catalyst can be commonly used in the art various have adsorb desulfidation
Catalyst, is preferably the catalyst with absorption desulfidation using zinc oxide as active component.Can be such as
The catalyst with absorption desulfidation disclosed in CN1208124C and CN1331591C.
The described granularity of catalyst with absorption desulfidation can be conventional selection, is as the criterion being capable of fluidisation.
Usually, the granularity of the catalyst described in absorption desulfidation can be 20～150 microns.In the present invention, catalyst
Granularity is volume average particle sizes, uses laser particle size analyzer to measure.
The method according to the invention, described sulfur-bearing hydrocarbon feed contacts with the described catalyst with absorption desulfidation
The atmosphere of hydrogen is carried out.Hydrogen charging aperture bottom described fluidized-bed reactor together with sulfur-bearing hydrocarbon feed can be sent
In the reaction zone of fluidized bed reactor.The consumption of described hydrogen can be the conventional selection of this area.Usually, described fluidisation
In the charging of bed reactor, hydrogen can be 0.1～2:1 with the mol ratio of sulfur-bearing hydrocarbon feed, preferably 0.15～1.5:1, more
It is preferably 0.2～1:1.In described reactor, the superficial gas velocity with hydrogen of sulfur-bearing hydrocarbon feed can be 0.1～0.6m/s.
The method according to the invention is for the condition contacted with the catalyst with absorption desulfidation by sulfur-bearing hydrocarbon feed
It is not particularly limited, can carry out under the normal condition of this area, the element sulphur in described sulfur-bearing hydrocarbon feed can be taken off
Except being as the criterion to meeting requirement.Usually, the temperature of described contact can be 300～500 DEG C, preferably 320～480 DEG C；With absolutely
Pressure meter, the pressure in described fluidized-bed reactor can be 0.5～5MPa, preferably 1.0～4.5MPa；Described sulfur-bearing hydrocarbon feed
Weight (hourly) space velocity (WHSV) can be 1～15h-1, preferably 2～12h-1。
The present invention is not particularly limited for reclaimable catalyst is carried out regeneration method, can be the conventional choosing of this area
Select, such as, can regenerate according to the method disclosed in CN1323137C.Specifically, can be by reclaimable catalyst oxygenous
Regenerating in atmosphere, the condition of described regeneration includes: temperature can be 350～650 DEG C；In terms of absolute pressure, pressure can be 240～
1134kPa；The superficial linear vilocity of oxygen-containing gas can be 0.2～1.5m/s.
The present invention, can be in the routine of this area for the method that regenerated catalyst carries out reducing also being not particularly limited
Under the conditions of reduce.Usually, can contact with the gas of hydrogen by making regenerated catalyst, thus by regenerated catalyst
Reduction.The condition of described reduction can be conventional selection.Usually, the condition of described reduction includes: temperature can be 300～
550℃；In terms of absolute pressure, pressure can be 800～3000kPa；The superficial linear vilocity of hydrogen-containing gas can be 0.1～1.5m/s.
The consumption of described hydrogen is can be as the criterion the catalyst reduction after regeneration.
The method according to the invention, before regenerated catalyst being sent into and reducing in catalyst reducer, preferably uses
Nitrogen strips, to remove the oxygen carried secretly in regenerated catalyst.Described stripping can enter in regenerated catalyst receptor
OK.The present invention is not particularly limited for described steam stripped condition, can be the conventional selection of this area, can remove regeneration
The oxygen carried secretly in catalyst is as the criterion.
The present invention is described in detail below in conjunction with embodiment.
Following example if not otherwise specified, use the absorption desulfuration reaction device shown in Fig. 1 to carry out sulfur-bearing hydrocarbon feed
Absorption desulfurization.Wherein: the reaction zone of fluidized-bed reactor includes straight tube district and expanding district from bottom to top, the internal diameter in straight tube district is
60mm, the outer contour in expanding district and the angle of horizontal plane are 45 °, and the internal diameter of decanting zone is 150mm, and the height of reaction zone is
2000mm, the height of decanting zone is 1000mm.
In following example and comparative example, if not otherwise specified, fine powder collector is metal filter candle filter, wherein, by 2
Root rustless steel chimney filter is installed in parallel in a cylindrical housings, enters rustless steel filter from the oil preparation product of fluidized-bed reactor output
In the shell side of pipe, the internal diameter of rustless steel chimney filter is 80mm, a length of 400mm, and the average pore size of the through hole on body is 5 microns；
The internal diameter of housing is 300mm.
In following example and comparative example, use commercially available from Malvern company laser particle size analyzer measure granularity and
Particle mean size, wherein, particle mean size is volume average particle sizes.
In following example and comparative example, nitrogen adsorption static volumetric method is used to measure specific surface area and the hole body of catalyst
Long-pending.
In following example and comparative example, pressure differential method method is used to measure dilute phase density in fluidized-bed reactor decanting zone.
Embodiment 1～4 is used for the present invention is described.
Embodiment 1
In the present embodiment, the structure of fluidized-bed reactor is as follows.
(1) top of decanting zone is provided with the first cyclone type gas-solid separator and the separation of the second cyclone type gas-solid of nesting
Device, the top of the first cyclone type gas-solid separator connects with the top of the second cyclone type gas-solid separator, wherein, two spiral-flow types
Tangentially being each provided with 4 in the straight tube district of gas-solid separator and guide air intake passage, described guiding air inlet is in described straight tube district
Circumferencial direction for being uniformly arranged；
(2) contour line that cross section is square and guiding air intake passage guiding air intake passage is logarithmic spiral song
Line, any on described guiding air intake passage arrival end and described guiding air intake passage the port connected with described straight tube district
The straight line that the upper point corresponding with this point determines is 30 ° with the angle theta of horizontal plane；
The area of the arrival end guiding air intake passage is A231=200mm2, guide what air intake passage connected with described straight tube district
The area of port is A232, A231/A232=1.3；
The height in straight tube district is H21=400mm, the height of pyramidal area is H22, H21/H22=0.7；
The internal diameter D of airway4=15mm, the guiding air intake passage on the lower edge of airway to the second cyclone type gas-solid separator
The distance on lower edge be H1, H1/D4=0.5；
The extension in the discharging opening of the first cyclone type gas-solid separator of the discharging opening of the second cyclone type gas-solid separator is long
Degree is L224, a length of L of the discharging opening of the first cyclone type gas-solid separator214, L224/L214=0.7；
(3) set between the straight tube district of the straight tube district of the first cyclone type gas-solid separator and the second cyclone type gas-solid separator
Being equipped with kuppe, the internal diameter of kuppe is D3, the internal diameter in the straight tube district of described first cyclone type gas-solid separator is D211, described
The internal diameter in the straight tube district of the second cyclone type gas-solid separator is D221, D211: D3: D221=1.4:1:0.5；The height of described kuppe
For H3=250mm, the height in the straight tube district of described first cyclone type gas-solid separator is H211, described second cyclone type gas-solid separates
The height in the straight tube district of device is H221, H211: H3: H221=1.9:1:0.5.
The gross area of the arrival end guiding air intake passage on (4) first cyclone type gas-solid separators is At 23, described sedimentation
The area of the horizontal cross-section in district is A12, the area of the radial section of described airway is A4, At 23: A12: A4Preferably 0.05:1:
0.25。
(5) between reaction zone and decanting zone, it is provided with two spaced inner members (as shown in Figure 7), inner member
Outer ring plate connects with the inwall of reactor body, and the baffle plate of inner member and the angle of horizontal plane are 45 °；Between two inner members
Distance is 10mm, and inner member below is 100mm with the distance on beds surface.
In the present embodiment, idiographic flow is as follows.
Hydrogen and sulfur-bearing hydrocarbon feed (for sour gasoline, character is listed in table 2) are passed through material with the mol ratio of 0.2:1
Input pipe 5 is sent in the reaction zone of fluidized-bed reactor (superficial gas velocity is 0.38m/s), with the catalysis with absorption desulfidation
(the S Zorb catalyst that middle petrochemical industry Nanjing catalyst plant produces, the trade mark is FCAS-R09, and the character of catalyst arranges in Table 1 in agent
Go out) contact, to remove at least part of element sulphur in sulfur-bearing hydrocarbon feed.Wherein, absorption desulfurization condition includes: the temperature of contact is
400 DEG C, in terms of absolute pressure, pressure is 2.6MPa, and the weight (hourly) space velocity (WHSV) of sulfur-bearing hydrocarbon feed is 4h-1。
Table 1
Table 2
The oil agent mixture that contact obtains enters cyclone type gas-solid separator by decanting zone and (divides at the first cyclone type gas-solid
From device guide air inlet arrival line speed be 3m/s) in separate.Carry secretly from cyclone type gas-solid separator is isolated
The gas mixture having catalyst fines is entered in fine powder collector by airway and is further separated, and obtains oil gas
Product and recovery catalyst, during the catalyst of recovery disclosure satisfy that when use requires, reaction zone is sent in circulation, otherwise send into catalysis
In agent fine powder storage tank；Oil gas product exports subsequent separation system.
After reclaimable catalyst regenerates in a regenerator, send in catalyst reducer and reduce, urging after reduction
Agent reenters in the reaction zone of fluidized-bed reactor.Wherein, the condition of regeneration includes: temperature is 510 DEG C；In terms of absolute pressure,
Pressure is 400kPa；The superficial linear vilocity of oxygen-containing gas is 0.45m/s；The condition of reduction includes: temperature is 400 DEG C；With absolute pressure
Meter, pressure is 3MPa；The superficial linear vilocity of hydrogen-containing gas is 0.4m/s.
It is carried out continuously 500 hours.In course of reaction, monitor following index: the composition of the oil gas product that (1) obtains；(2) urge
The particle mean size of the catalyst in agent fine powder storage tank and fluidized-bed reactor inner catalyst dense-phase bed；(3) fluidized-bed reaction
Dilute phase density in device decanting zone, result is listed in table 3.
After reacting 500 hours, in the catalyst in dense-phase bed in fluidized-bed reactor, granularity is less than the catalysis of 30 μm
The content of agent is 6.5 weight %.2kg catalyst fines collected by 500 hours rear catalyst fine powder storage tanks.
Table 3
*: on the basis of the anti-knock index as the sour gasoline of hydrocarbon feed, wherein, anti-knock index=(RON+MON)/2
Embodiment 2
Use method same as in Example 1 to carry out adsorbing desulfurization, except for the difference that, do not set between reaction zone and decanting zone
Put inner member.
It is carried out continuously 500 hours.In course of reaction, monitor following index: the composition of the oil gas product that (1) obtains；(2) urge
The particle mean size of the catalyst in agent fine powder storage tank and fluidized-bed reactor inner catalyst dense-phase bed；(3) fluidized-bed reaction
Dilute phase density in device decanting zone, result is listed in table 4.
After reacting 500 hours, in the catalyst in dense-phase bed in fluidized-bed reactor, granularity is less than the catalysis of 30 μm
The content of agent is 5.9 weight %.2.5kg catalyst fines collected by 500 hours rear catalyst fine powder storage tanks.
Table 4
*: on the basis of the anti-knock index as the sour gasoline of hydrocarbon feed, wherein, anti-knock index=(RON+MON)/2
Comparative example 1
Using method same as in Example 2 to carry out adsorbing desulfurization, except for the difference that, reactor decanting zone arranges dust-filtering
Device (this dust filter unit is metal filter candle formula filter) replaces cyclone type gas-solid separator, from the oil of fluidized-bed reactor output
Gas mixture directly exports.
It is carried out continuously 500 hours.In course of reaction, monitor following index: the composition of the oil gas product that (1) obtains；(2) stream
The particle mean size of the catalyst in fluidized bed reactor inner catalyst dense-phase bed；(3) dilute phase in fluidized-bed reactor decanting zone
Density, result is listed in table 5.
After reacting 500 hours, in the catalyst in dense-phase bed in fluidized-bed reactor, granularity is less than the catalysis of 30 μm
The content of agent is 6.1 weight %.Further, owing in system, fine powder content increases, between the metal dust chimney filter blowback of reactor head
Every shortening, have a strong impact on the operation of device.
Table 5
*: on the basis of the anti-knock index as the sour gasoline of hydrocarbon feed, wherein, anti-knock index=(RON+MON)/2
Comparative example 2
Using method same as in Example 1 to carry out adsorbing desulfurization, except for the difference that, the guiding of cyclone type gas-solid separator is entered
Material passage only one of which, cross section is square straight tube, and cross-sectional area is 150mm2.Oil agent mixture in decanting zone with
The speed of 18m/s enters and guides air intake passage.
It is carried out continuously 500 hours.In course of reaction, monitor following index: the composition of the oil gas product that (1) obtains；(2) stream
The particle mean size of the catalyst in fluidized bed reactor inner catalyst dense-phase bed；(3) dilute phase in fluidized-bed reactor decanting zone
Density, result is listed in table 6.
After reacting 500 hours, in the catalyst in dense-phase bed in fluidized-bed reactor, granularity is less than the catalysis of 30 μm
The content of agent is 7 weight %.6kg catalyst fines collected by 500 hours rear catalyst fine powder storage tanks.
Table 6
*: on the basis of the anti-knock index as the sour gasoline of hydrocarbon feed, wherein, anti-knock index=(RON+MON)/2
Embodiment 3
Method same as in Example 1 is used to carry out adsorbing desulfurization, except for the difference that:
Connected with described straight tube district by any on described guiding air intake passage arrival end and described guiding air intake passage
Port on the angle of the straight line that determines of the point corresponding with this point and horizontal plane be 5 °；
The area of the arrival end guiding air intake passage is A231=200mm2, guide what air intake passage connected with described straight tube district
The area of port is A232, A231/A232=2；
Absorption desulfurization condition include: the temperature of contact is 420 DEG C, and in terms of absolute pressure, pressure is 4MPa, sulfur-bearing hydrocarbon feed with
The speed of 0.3m/s enters reactor, and the oil agent mixture in decanting zone enters with the speed of 3.5m/s and guides air intake passage.
It is carried out continuously 500 hours.In course of reaction, monitor following index: the composition of the oil gas product that (1) obtains；(2) urge
The particle mean size of the catalyst in agent fine powder storage tank and fluidized-bed reactor inner catalyst dense-phase bed；(3) fluidized-bed reaction
Dilute phase density in device decanting zone, result is listed in table 7.
After reacting 500 hours, in the catalyst in dense-phase bed in fluidized-bed reactor, granularity is less than the catalysis of 30 μm
The content of agent is 7.0 weight %.2.1kg catalyst fines collected by 500 hours rear catalyst fine powder storage tanks.
Table 7
*: on the basis of the anti-knock index as the sour gasoline of hydrocarbon feed, wherein, anti-knock index=(RON+MON)/2
Embodiment 4
Using method same as in Example 1 to carry out adsorbing desulfurization, difference is as follows.
Connected with described straight tube district by any on described guiding air intake passage arrival end and described guiding air intake passage
Port on the angle of the straight line that determines of the point corresponding with this point and horizontal plane be 15 °.
The area of the arrival end guiding air intake passage is A231=250mm2, guide what air intake passage connected with described straight tube district
The area of port is A232, A231/A232=1.5。
The height in straight tube district is H21=300mm, the height of pyramidal area is H22, H21/H22=0.5。
The internal diameter of airway is D4=20mm, the guiding air intake on the lower edge of airway to the second cyclone type gas-solid separator leads to
The distance on the lower edge in road is H1, H1/D4=1。
The extension in the discharging opening of the first cyclone type gas-solid separator of the discharging opening of the second cyclone type gas-solid separator is long
Degree is L224, a length of L of the discharging opening of the first cyclone type gas-solid separator214, L224/L214=0.5。
Arrange between the straight tube district of the straight tube district of the first cyclone type gas-solid separator and the second cyclone type gas-solid separator
Having kuppe, the external diameter of described kuppe is D3, the internal diameter in the straight tube district of described first cyclone type gas-solid separator is D211, institute
The external diameter in the straight tube district stating the second cyclone type gas-solid separator is D221, D211: D3: D221=1.5:1:0.6；The height of described kuppe
Degree is H3, the height in the straight tube district of described first cyclone type gas-solid separator is H211, described second cyclone type gas-solid separator
The height in straight tube district is H221, H211: H3: H221=1:1:0.6.
The gross area of the arrival end guiding air intake passage on the first cyclone type gas-solid separator is At 23, described decanting zone
The area of horizontal cross-section be A12, the area of the radial section of described airway is A4, At 23: A12: A4Preferably 0.1:1:
0.04。
Oil agent mixture in decanting zone enters with the speed of 5m/s and guides air intake passage.
Absorption desulfurization condition include: the temperature of contact is 380 DEG C, and in terms of absolute pressure, pressure is 2MPa, sulfur-bearing hydrocarbon feed with
The speed of 0.3m/s enters reactor.
It is carried out continuously 500 hours.In course of reaction, monitor following index: the composition of the oil gas product that (1) obtains；(2) urge
The particle mean size of the catalyst in agent fine powder storage tank and fluidized-bed reactor inner catalyst dense-phase bed；(3) fluidized-bed reaction
Dilute phase density in device decanting zone, result is listed in table 8.
After reacting 500 hours, in the catalyst in dense-phase bed in fluidized-bed reactor, granularity is less than the catalysis of 30 μm
The content of agent is 6.6 weight %.2.3kg catalyst fines collected by 500 hours rear catalyst fine powder storage tanks.
Table 8
*: on the basis of the anti-knock index as the sour gasoline of hydrocarbon feed, wherein, anti-knock index=(RON+MON)/2
The result of embodiment 1～4, can it can be seen that use the absorption desulfuration reaction device of the present invention to carry out adsorbing desulfurization
To be effectively reduced sulfur content in sulfur-bearing hydrocarbon feed, reach the purpose of desulfurization.
From the result of embodiment 1 and comparative example 1 it can be seen that embodiment 1 is during continuously running, dilute in decanting zone
Under phase density and stable, therefore the absorption desulfuration reaction device of the present invention can be effectively reduced fluidized-bed reactor settlement space
Granule suspended concentration, the cycle of oparation of extension fixture.
Embodiment 1 is compared with comparative example 2 it can be seen that compared with comparative example 2, the catalyst in embodiment 1 is thin
The particle mean size of the catalyst in powder storage tank is bigger, illustrates compared with traditional cyclone separator, and the absorption desulfurization of the present invention is anti-
Answer the cyclone type gas-solid separator in device little to the abrasion of catalyst granules, it is possible to reduce the consumption of catalyst.
Embodiment 1 and embodiment 2 are compared it can be seen that pass through in the decanting zone of fluidized-bed reactor and reaction zone
Between inner member is set, it is possible to reduce further the suspended catalyst concentration in decanting zone.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy illustrates the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (20)
1. an absorption desulfuration reaction device, this device includes fluidized-bed reactor, fine powder collector, regenerator and restorer,
Described fluidized-bed reactor is for contacting sulfur-bearing hydrocarbon feed with the catalyst with absorption desulfidation, and exports oil preparation mixing
Thing；Described fine powder collector is for isolating the catalyst fines in described oil agent mixture；Described regenerator will be for inactivating
Catalyst regeneration；Described restorer is for sending into the catalyst reduction Posterior circle of regeneration in described fluidized-bed reactor；
It is characterized in that, described fluidized-bed reactor includes reactor body, at least one the cyclone type gas-solid separator sealed
And airway；
The inner space of described reactor body includes reaction zone and decanting zone from bottom to top；
The main body of described cyclone type gas-solid separator is the hollow structure that top seals, and its inner space includes straight tube from top to bottom
District and pyramidal area, the main body of described cyclone type gas-solid separator is arranged in described decanting zone, described cyclone type gas-solid separator
Discharging opening be positioned at the bottom of described pyramidal area and extend downward in described reaction zone, the air inlet of described airway is positioned at institute
Stating in straight tube district, the gas outlet of described airway is positioned at the outside of described fluidized-bed reactor, and the top in described straight tube district is along cutting
Guiding air intake passage to being provided with at least two, the contour line of described guiding air intake passage is spiral curve.
Absorption desulfuration reaction device the most according to claim 1, wherein, described spiral curve is logarithmic spiral curve.
Absorption desulfuration reaction device the most according to claim 1, wherein, the quantity of described guiding air intake passage is 3～8
Individual.
4. according to the absorption desulfuration reaction device described in any one in claims 1 to 3, wherein, described guiding air intake passage
For being uniformly arranged on the circumferencial direction in described straight tube district.
5. according to the absorption desulfuration reaction device described in any one in claims 1 to 3, wherein, described guiding air intake lead to
On road arrival end a little and the described guiding air intake passage point corresponding with this point with on the port that described straight tube district connects
The straight line determined is 0～45 ° with the angle of horizontal plane.
6. according to the absorption desulfuration reaction device described in any one in claims 1 to 3, wherein, described guiding air intake passage
The area of arrival end be A231, the area of the port that described guiding air intake passage connects with described straight tube district is A232, A231/A232
=1～5.
Absorption desulfuration reaction device the most according to claim 1, wherein, described cyclone type gas-solid separator includes the first rotation
Streaming gas-solid separator and the second cyclone type gas-solid separator, described second cyclone type gas-solid separator is arranged on described first rotation
In the main body of streaming gas-solid separator, the air inlet of described airway is positioned at the straight tube district of described second cyclone type gas-solid separator
In.
Absorption desulfuration reaction device the most according to claim 7, wherein, the discharging of described second cyclone type gas-solid separator
Mouth development length in the discharging opening of described first cyclone type gas-solid separator is L224, described first cyclone type gas-solid separates
The a length of L of the discharging opening of device214, L224/L214=0.4～1.
9. according to the absorption desulfuration reaction device described in claim 1 or 7, wherein, the internal diameter of described airway is D4Lead described in,
The lower edge of trachea is H to the distance on the lower edge guiding air intake passage of described cyclone type gas-solid separator1, H1/D4=0～10.
10. according to the absorption desulfuration reaction device described in claim 1 or 7, wherein, at least one cyclone type gas-solid separator
Being provided with kuppe in straight tube district, described kuppe is tubular, the upper end of described kuppe and this cyclone type gas-solid separator
Top connects, and the lower end of described kuppe is uncovered.
11. absorption desulfuration reaction devices according to claim 10, wherein, described kuppe is arranged on described first eddy flow
In the straight tube district of formula gas-solid separator, and the straight tube district of the outer wall of described kuppe and described first cyclone type gas-solid separator
, between inwall and the outer wall of described second cyclone type gas-solid separator of described kuppe, there is sky in Existential Space between inwall
Between.
12. absorption desulfuration reaction devices according to claim 10, wherein, the internal diameter of described kuppe is D3, described first
The internal diameter in the straight tube district of cyclone type gas-solid separator is D211, the internal diameter in the straight tube district of described second cyclone type gas-solid separator is
D221, D211: D3: D221=1.25～2.5:1:0.4～0.8.
13. absorption desulfuration reaction devices according to claim 10, wherein, the height of described kuppe is H3, described
The height in the straight tube district of one cyclone type gas-solid separator is H211, the height in the straight tube district of described second cyclone type gas-solid separator
For H221, H211: H3: H221=1～2.5:1:0.4～1.
14. according to the absorption desulfuration reaction device described in any one in claims 1 to 3 and 7, wherein, for receive from
The gross area of the arrival end guiding air intake passage of the logistics in decanting zone is At 23, the area of the horizontal cross-section of described decanting zone
For A12, the area of the radial section of described airway is A4, At 23: A12: A4=0.01～0.4:1:0.01～0.4.
15. absorption desulfuration reaction devices according to claim 1, wherein, described fluidized-bed reactor also includes at least one
Individual inner member, described inner member is arranged on described reaction zone and the intersection of described decanting zone, and described inner member includes fixed plate
And multiple baffle plate, the two ends of described baffle plate are fixing with described fixed plate respectively to be connected, and described fixed plate is along reactor body
Longitudinally disposed and fixing with reactor body be connected, described baffle plate is along the horizontally set of described reactor body and relative to level
Face is for being obliquely installed, and adjacent screen is arranged for interval, and the relevant position of described inner member is provided with to be divided for described cyclone type gas-solid
The hole passed through from the discharging opening of device.
16. absorption desulfuration reaction devices according to claim 15, wherein, described baffle plate inclination angle with respect to the horizontal plane
Degree makes the projection in the horizontal plane of the lower edge of the projection in the horizontal plane of the upper edge of baffle plate and adjacent screen overlap.
17. according to the absorption desulfuration reaction device described in claim 15 or 16, and described fixed plate includes outer ring plate and mutually hangs down
Straight two dividing plates arranged, described dividing plate be arranged in the space that outer ring plate surrounds and two ends respectively with the inwall of described outer ring plate
Fixing connection, the two ends of described baffle plate are fixing with the inwall of described outer ring plate and described dividing plate respectively to be connected.
18. 1 kinds of desulfurizing method by adsorption, the method absorption desulfuration reaction device described in any one in claim 1～17
In carry out, including: by sulfur-bearing hydrocarbon feed with have absorption desulfidation catalyst in the reaction zone of described fluidized-bed reactor
Middle contact, to remove at least part of element sulphur in described sulfur-bearing hydrocarbon feed；The oil agent mixture that fluidized-bed reactor is exported
Fine powder collector separates, obtains the catalyst fines of oil gas product and recovery；The catalyst that will at least partly reclaim
Fine powder circulation is sent in described reaction zone；Decaying catalyst is sent in described regenerator and regenerates, obtain regenerated catalyst；
In in the described regenerated catalyst described restorer of feeding, reduction Posterior circle sends into the reaction zone of described fluidized-bed reactor.
19. methods according to claim 18, wherein, the temperature of described contact is 300～500 DEG C；In terms of absolute pressure, described
Pressure in fluidized-bed reactor is 0.5～5MPa；The weight (hourly) space velocity (WHSV) of described sulfur-bearing hydrocarbon feed is 1～15h-1。
20. according to the method described in claim 18 or 19, wherein, described sulfur-bearing hydrocarbon feed be direct steaming gasoline, catalytic gasoline and
One or more in coker gasoline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310528628.4A CN104593053B (en) | 2013-10-31 | 2013-10-31 | Adsorption desulphurization reaction apparatus and adsorption desulphurization method |
Applications Claiming Priority (1)
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| CN101434862A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Method for reducing sulfide in light hydrocarbon oil |
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| CN101134916A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Catalytic hydroprocessing adsorping desulfurization for hydrocarbon oil in fluidized reactor |
| CN101434862A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Method for reducing sulfide in light hydrocarbon oil |
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